Development of Mixed-Salt Technology for CO Capture From

Development of Mixed-Salt Technology for CO2 Capture from Coal Power Plants

Presented by: Indira S. Jayaweera Sr. Staff Scientist and CO2 Program Leader SRI International, CA, USA

FE0012959 SRI Kick-off Meeting December 11, 2013

© 2013 SRI International Discussion Topics • Project Background – Brief overview of SRI & Short discussion of research leading to this award • Project Objectives • Project Team • Project Structure • Project Schedule • Project Management Plan • Deliverables • Current Project Status • Questions • Closing Comments

© 2013 SRI International 2 Who We Are SRI is a world-leading R&D organization • An independent, nonprofit corporation – Founded by Stanford University in 1946 – Independent in 1970; changed name from Stanford Research Institute to SRI International in 1977 – Sarnoff Corporation acquired as a subsidiary in 1987; integrated into SRI in 2011 • Annual R&D Projects: ~ $600 million • More than 2,500 employees (~ 700 with advanced degrees) • More than 20 locations worldwide Silicon Valley - Headquarters Washington, D.C. Princeton, New Jersey Harrisonburg, Virginia

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© 2013 SRI International 4 SRI Incorporates a Facilitated CO2 Absorption in the New Mixed-Salt Process Potassium Carbonate-Based Ammonia-Based Processes Processes Pros Pros • Very high CO2 loading capacity, ~ 25 MW experience • No emissions, long-term experience • Reduced reboiler duty due to high-pressure • Many options are currently being tested regeneration • Easy permitting • Fast absorption-reaction kinetics

Cons Cons • Low efficiency and low CO2 loading • Large water-wash to reduce ammonia emission • Energy for solid dissolution • Solvent chilling requirements • Energy for water stripping (vacuum stripping) • Energy for solid dissolution SRI’s NOVEL MIXED SALT TECHNOLOGY (Low-Risk Approach: Advancement of known technologies) Reduced reboiler duty The new process has Reduced auxiliary electricity loads Reduced water use Enhanced absorption kinetics Reduced footprint Reduced emissions High CO2 loading High-pressure CO2 No Solids Reduce the CCS costs © 2013 SRI International 5 Improving Salt-Based CO2 Capture Systems

A generic process flow diagram (PFD) for solvent-based CO2 capture Need to reduce high energy penalties related to: • solvent chilling • solid dissolution (heat requirement for salt dissolution can be

up to 1MJ/ kg CO2) • water use for ammonia emission control • sour water stripper

© 2013 SRI International 6 Mixed-Salt Technology Process Conditions • Process uses mixtures of potassium carbonate and ammonium salts – Dual absorber and a selective regenerator – Heat of reaction 35 to 50 kJ/mol • Absorber operation at 20o – 40o C at 1 atm with ~ 38 wt.% mixture of salts • Regenerator operation at > 120oC at 20-40 atm

–Produce high-pressure CO2

CO2 Lean CO2 Rich

K2CO3–NH3–xCO2–H2O system  K2CO3 –NH3–yCO2–H2O system

Where y > x

>120°C 20 bar

- Absorber-side water C use reduced by more than order of magnitude

Ammonia vapor pressure as a function of CO2 loading. A comparison between mixed-salt and 10-m aqueous ammonia at 20°C is shown.

Performance (CO2 capture efficiency & CO2 loading) comparison for mixed salt and neat K2CO3 SRI WORK PRIOR TO APRIL 2013

Sources MEA Data: CSIRO Report (2012). EP116217 K2CO3 Data: GHGT-11; Schoon and Van Straelen (2011). TCCS-6

Process Comparison

Parameter Conventional SRI MEA Mixed Salt

Solution Circulation Rate 1 0.5 Regeranation Energy 1 0.5 Degradation of the Solvent 1 0 Solvent Loss 1 <0.1 Solvent Cost 1 <0.1 Corrosion Inhibitor YES NO Flue Gas Cooling YES YES FGD Requirement Deep FGD light FGD Hazardous Waste YES NO Oxygen tolarance NO YES

CO2 Loading 1 2

CO2 Pressure 1 20

Temp. °C

% CO2

Temp. °C

Diff. Pres. In.

Diff. water Temp. °C P

% CO2 MFC Air Flow lpm

MFC Cooling CO2 Flow lpm water Temp. °C Temp. °C Water

pH K2CO3 NH3 Solution Makeup Pump K2CO3 K2CO3 Metering 1- 5 gpm Blead NH3 NH3 Pump Rich Lean Solution Solution

Source for MEA data: DOE Award No. DE-FC26-02NT41440

• Presented at 25th ACS National Meeting, April 7-11, 2013, New Orleans, LA • Presented at 12th Annual CCUS Conference, May 12-16, 2013, Pittsburgh, PA • Presented at BIT’s 2nd Annual Clean Coal International Symposium of Clean Coal Technology, September 26-29, 2013, Xian, China • Filed a provisional patent in August 2012 • Filed the PCT application in November 2013

© 2013 SRI International 17 Discussion Topics • Project Background • DOE Project Objectives • Project Team • Project Structure • Project Schedule • Project Management Plan • Deliverables • Current Project Status • Questions • Closing Comments

© 2013 SRI International 18 Project Objectives The overall objective of the project is to develop and test a solvent-based CO2 technology that can capture CO2 from existing or new pulverized coal (PC) power plants at low cost Budget Period 1: • Demonstrate the absorber and regenerator processes individually with high efficiency and low NH3 emission and reduced water use compared to the state-of-the-art ammonia-based technologies Budget Period 2: • Demonstrate the high-pressure regeneration and integration of the absorber and the regenerator

• Demonstrate the complete CO2 capture system with low-cost production of CO2 stream, optimize the system operation, and collect data to perform the detailed techno-economic analysis of CO2 capture process integration to a full-scale power plant

Project Team and Organization

Project Team and Technical Leaders SRI- Indira Jayaweera; OLI Systems (OLI)- Andre Anderko; Stanford University - Adam Brant; Aqueous Systems Aps (ASAp)- Kaj Thomsen; Politechnico De Milano (POLIMI)- Gianluca Valenti; and Eli Gal © 2013 SRI International 20 Discussion Topics • Project Background • Project Objectives • Project Team • Project Structure – Budget Period (length and cost) – Description of Tasks by Budget Period • Project Schedule • Project Management Plan • Deliverables • Current Project Status • Questions • Closing Comments

Budget Period 1 Budget Period 2 Total 10/1/13 - 12/30/14 1/1/15 - 3/31/16 10/1/13-3/31/16 Total Project Cost $1,019,650 $1,102,092 $2,121,742 DOE Share $819,534 $878,113 $1,697,647 Cost Share $200,116 $223,979 $424,095

Cost share by SRI, OLI Systems, POLIMI, Aqueous Solutions Aps, Stanford University

© 2013 SRI International 22 Budget Period 1 Tasks Task 1: Project Management and Planning Task 2: Individual Absorber and Regenerator Testing in a Semi-Continuous Mode • System design, commissioning and performing parametric tests • Data analysis to determine the independent relationships between solvent concentration, absorption and regeneration conditions, column packing, CO2 capture efficiency, ammonia loss, and water usage • Provide data for process modeling Task 3: Preliminary Process Modeling and Techno-Economic Analysis. • UNIQUAC Model development by POLIMI and ASAp based on literature data • Establish a rate-based thermodynamic modeling database for potassium- and ammonium- based system heat and mass balance evaluations then transferred to Aspen Plus® • Establishing the basis for techno-economic analysis Task 4.0 - Budget Period 2 Continuation Application

Task 1: Project Management and Planning Task 5: Bench-Scale Integrated System Testing

• System design, commissioning and performing parametric tests (T, P, CO2 Loading) • Provide data for process modeling Task 6 - Process Modeling, Techno-Economic Analysis (TEA), and Technology EH&S Risk Assessment • A rate-based model for detailed mass-balance and heat-balance calculations for a flue gas feed equivalent to a 550-MWe flue gas stream will be developed • Aspen Plus® model to develop a process flow sheet of a PC-Power Plant (Cost Estimation Methodology for NETL Assessments of Power Plant Performance DOE/NETL 2011/1455 April 2011, Case 12) system (TEAM) • The process modeling and material balance and heat balance calculations will be based on updated rate-based modeling • Assessment of the environmental friendliness and safety of any future process based on the materials and process being developed (emissions, waste using DOE guidelines)

Mixed-Salt Technology for CO2 Capture: Simulation Studies

Andre Anderko

OLI Systems Inc. [email protected] Scope

• Summary of project tasks • Technology foundations • Thermophysical properties

 Results for selected subsystems of the K2CO3 – CO2 – NH3 – H2O system • Process simulation tools Project Tasks: Period 1

• Thermodynamic model for the system K2CO3 – CO2 – NH3 – H2O • Analysis of SRI test data for thermodynamic modeling • Process flowsheet using ESP (Electrolyte Simulation Program) • Absorber and regenerator modeled as equilibrium unit operations • Including mass transfer modeling • Transfer to Aspen+ for use by other team members Project Tasks: Period 2

• Heat and mass transfer modeling on the basis of SRI’s bench scale from budget period 1 data • Model optimization with budget period 2 data for full- scale heat- and mass-transfer modeling • Detailed rate-based model for mass and heat-balance calculations for flue gas stream Thermophysical Framework

Gas-phase Excess Gibbs Thermo- equation of chemistry of energy model state species

Standard-state Adsorption properties of Themodynamic models solution framework species

Phase and Transport chemical properties and equilibrium surface algorithm tension

Applications (process, corrosion, oilfield scaling, etc.)

Electrical Mixed-Solvent conductivity Electrolyte Viscosity Framework MSE thermo Standard- state: HKF Self - (direct) diffusivity ex ex ex ex GEX: MSE G GLR GLC GII Thermal = + + no limit on conductivity RT RT RT RT concentration LR Long-range electrostatic interactions Solid phases: Surface thermochemical LC Local composition term for tension properties neutral molecule interactions II Ionic interaction term for 2nd liquid phase: Interfacial tension specific ion-ion and ion- MSE (ionic) molecule interactions Interfacial phenomena: ion exchange, surface complexation, molecular adsorption Thermodynamic Fundamentals: Mixed-Solvent Electrolyte (MSE) Model

80 • Prediction of phase

70 equilibria and K2CO3 K2CO3·1.5H2O 60 thermodynamic

50 properties in wide

40 K2CO3·6H2O temperature and

30 composition

20 ranges

K2CO3,weight % 10 Ice • Example: solid- K2CO3 + H2O 0 liquid boundaries -40 -20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 for the binary Temperature, C system K2CO3 – H2O Vapor-liquid equilibria:

K2CO3 – KHCO3 – CO2 – H2O • The model Carbon Dioxide Partial Pressure of 20 wt% Potassium reproduces: Carbonate 1 40C • VLE 50C • SLE 0.1 60C 70C • Heats of mixing 80C and dilution 0.01 • Heat capacity 0.001 • Density • Ionic equilibria

CO2Pressure, Partial atm 0.0001 0 0.1 0.2 0.3 0.4 0.5 moles CO2 / mole K2CO3 Aqueous Ammonia / Carbon Dioxide Pressure at 100 100 C for mNH3 Vapor-liquid

1.0m equilibria: 2.0m 10 3.9m NH3 – CO2 – H2O 6.0m 7.3m 8.0m Pressure,atm 9.6m • Total and partial 11.0m pressures 1 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 • Phase equilibria CO2/NH3, m/m combined with Aqueous Ammonia / Carbon Dioxide Partial Pressures at 20 C for mNH3 chemical equilibria 1 0.1m 0.5m • Acid-base 1.0m equilibria 0.1 2.2m • Complex 0.01 (carbamate) formation 0.001

PNH3,PCO2, atm

0.0001 0 0.2 0.4 0.6 0.8 1 CO2/NH3, m/m Mass transfer separations

• Heat and mass-transfer correlations 2.5

/s Dexp H2O • Properties for predicting 2 2.0 Dcal H2O

heat and mass transfer O)m 1.5 2 • Diffusivity

D(H 1.0 9

• Viscosity 10 0.5

• Thermal conductivity 0.0 • Surface tension 0.0 1.0 2.0 3.0 0.5 • Density m -K2CO3 Self-diffusion coefficient

of H2O in K2CO3 solutions Conclusions

• Thermodynamics

• OLI’s MSE model represents the properties of H2O – CO2 – salt mixtures up to saturation or fused salt limit • Complete parameterization needs to be developed for the K2CO3 – CO2 – NH3 – H2O system based on literature and SRI plant data • Process simulation • ESP: A convenient simulator for modeling the process

 Equilibrium treatment

 Mass-transfer-based algorithm • Interfaces to third-party process simulators

Power Plant Integration with the CC Plant

Fresh Water

Reduce NOx Reduce Ash Reduce Sulfur

Coal PC Boiler SCR ESP FGD Air Flue Gas Stack Fly Ash Gypsum/Waste Heat Integration

Steam CO2 Turbine Removal

CO2 Compression and Storage, EOR, or other use

Heat Integration Alternative Options Ideas: Stanford Modeling of CC power plant steam cycle integration with the CC plant: POLIMI in support by ASAps

The CO2 capture plant is simulated with Aspen Plus and called the Extended UNIQUAC model

The power plant is simulated with the in-house code named GS

The Aspen Plus and GS integration is managed manually as follows:  composition of exhaust gas is calculated in GS and written once in Aspen  temperatures and flow rates of extracted steam to the reboiler and condensed water from the reboiler are calculated in Aspen Plus  extracted steam is released to the turbine in GS  condensed water is released to an appropriate feed water preheater or to the cycle condenser in GS  net electricity production is computed as the difference between:  the electricity production of the power plant from GS (which includes the loss due to steam extraction)  the electricity consumption of capture plant from Aspen Plus Discussion Topics • Project Background • Project Objectives • Project Team • Project Structure • Project Schedule • Project Management Plan – Milestones – Risk Management • Deliverables • Current Project Status • Questions • Closing Comments

Complexity of the Mixed-Salt Process: The technology uses a two-stage absorber system. The program is structured first to optimize the absorber conditions using two individual absorbers in budget period 1 before attempting to test a single two-stage absorber. This approach is designed to improve the process performance and also to reduce the cost. © 2013 SRI International 41 Deliverables Reports Providing • Absorption/Desorption Isotherms covering the full range of operating pressures and temperatures considered for capturing CO2 from coal-derived flue gas • Experimental results from bench-scale activities, including: – measured heat and mass-transfer data – measured reaction kinetics data • Updated state-point data table, including measured data

• Identification of flue-gas clean-up requirements upstream of the CO2 capture process • Recommended system operating pressures, temperatures, and working capacity • Fate of solvent • Identification of suitable process configuration(s) for commercial-scale operations including description of absorption/desorption models used to predict equipment performance and capacity (TEA Report) • Process hazard evaluation (EH&S Report)

© 2013 SRI International 42 Discussion Topics • Project Background • Project Objectives • Project Team • Project Structure • Project Schedule • Project Management Plan • Deliverables • Current Project Status • Questions • Closing Comments

• Subcontracts awards were made last week • Program management plan updated • Absorber design in progress • Regenerator modification design in progress • Bi-weekly webex meetings to be resumed starting January 13

Preliminary Regenerator Design Existing System

All analyses are done in house Custom data acquisition

4.0 0.25 MMeasuredeasured R ([NH3]aq = 0.1 - 0.2 M) Palitha's model ( [NH3]aq = 0.05 - 0.1 m) ModelPalitha's 1model ([NH3]aq = 0.2 m) 3.5 Model 2

3.0 2 R = 227.23 - 50.493*pH + 2.8232*(pH) Loading

2.52 CO 0.502.0

0.661.5

S-Building Building: SRI 6 MW Plant Large bench and mini-pilot studies CO2 yard for mini- pilot testing (up to 100 acfm)

Physical Science Building: Lab- scale tests

SRI’s site in Menlo Park, CA (~ 65 acres) SRI also has a test site near Livermore, CA (480 acres)

© 2013 SRI International 48 Discussion Topics • Project Background • Project Objectives • Project Team • Project Structure • Project Schedule • Project Management Plan • Deliverables • Current Project Status • Questions • Closing Comments

Dr. Indira Jayaweera, Sr. Staff Scientist and CO2 Program Leader indira,[email protected] SRI International 333 Ravenswood Avenue 1-650-859-4042 Menlo Park, CA 94025-3493 650.859.2000 Dr. Marcy Berding, Director, Materials Research Laboratory [email protected] Washington, D.C. 1-650-859-4267 SRI International 1100 Wilson Blvd., Suite 2800 Arlington, VA 22209-3915 703.524.2053

Princeton, New Jersey

SRI International Sarnoff 201 Washington Road Princeton, NJ 08540 609.734.2553

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